Tetraphosphoric acid esters



Planes Sept: 6, 1938 Pram orrica TETRAPHOSPHORIC ACID ESTERS Morris B.Katzman, Chicago, Ill.

No Drawing. Application April 9, 1927,

' Serial No. 135,931

23 Claims.

r employed in a treating bath containing textile,

Cil

leather or ores. Many of the compounds of my invention are alsoeffective to decrease the spattering of margarine, to increase theoiliness of lubricating oils and greases, such as are derived frommineral oils, to act as emulsifying agents for cosmetic and otheremulsions, to reduce vis-- cosity of chocolate and the like, to retardthe rancidification of oils, fats, and vitamin preparations which aresubject to deterioration by oxidation, to act as assistants in thetextile and related industries and, 'in general, to function whereverinterface modification is sought or desired.

The substances of my invention have many useful application in the artswhere frothing, foaming, wetting, penetrating, detergent, emulsifying,and other interface modifying functions are required. They are ingeneral possessed of at least two groups, one having a hydrophilefunction and the other having a lipophile function in the molecule. Thehydrophile function is performed primarily by a tetra-phosphoric acid ortetraphosphate group, giving the molecule as a whole an affinity foraqueous materials.

The lipophile group is any radical having a clefinite aflinity for oilsand fats and may comprise. radicals such as acyl or alkyl derived from afatty acid or its corresponding alcohol. The hydrophile tetraphosphategroup may be and preferably is linked to the lipophile group by means ofa polyhydroxy substance. I have found polyhydroxy substances such assugars, sugar alcohols, glycols, polyglycols, glycerol, polyglycerols,and hydroxycarboxylic acids to be particularly suitable. An esterlinkage joins the polyhydroxy substance and the tetra-phosphate group.The linkage between the polyhydroxy substance and the lipophile groupmay be either an ester or ether linkage.

All of the products of my invention, as indicated, are esters oftetraphosphoric acid, which acid may be represented by the followingstructural formula: I

More specifically, the most preferable of the compounds of my inventionmay be defined as tetraphosphoric acid esters of polyhydroxy substanceswherein at least one hydroxy group of the polyhydroxy substance has itshydrogen substituted by a lipophile group. The lipophile group mayinclude any organic acid group, particularly fatty acid groups havingpreferably at least four carbon atoms such as the fatty acid radicals ofthe following acids: caproic acid, caprlc, caprylic, valeric, butyric,abietic, naphthenic, hydroxystearic, benzoic, benzoylbenzoic, naphthoic,toluic, higher molecular weight saturated and unsaturated fatty acidsincluding palmitic acid, stearic, lauric, melissic, oleic, myristic,ricinoleic, linoleic acid or mixed fatty acids derived from animal orvegetable fats and fishcils such as lard,-oleo oil, coconut oil, cornoil, cottonseed oil, partially or completely hydrogenated vegetable oilssuch as cottonseed oil, corn oil, sesame oil and fatty acids of variouswaxes such as beeswax and carnauba wax; or the lipophile group may be analkyl radical derived from an alcohol corresponding to any of thepreceding acids, such as octanol, cetyl alcohol, stearyl alcohol, oleylalcohol, lauryl alcohol, higher saturated and unsaturated aliphaticalcohols derived from natural fats and oils, cholesterol, sperm oil,etc.

Specific examples of polyhydroxy substances,

the residues of which may serve as linkages between the lipophile groupsand the hydrophile tetraphosphate groups, besides those previouslymentioned, are as follows: mucic acid, tartaric acid, saccharic acid,gluconic acid, glucuronic acid, gulonic acid, mannoic acid,trihydroxyglutaric acid, glyceric acid, and the like, as well ascarboxylic oxidation products of polyglycerols which may be representedby the formulae:

7 on on o ao-onl-dn-onr-o.oni-t in-i z-oa on on on oHo-cm-dn-cm-o-om-dn-cnro-onz-cu-ti-on n I nlie-0-tin-on,-o-ora-on-cm-o-cm-o-oa and sugars such as: xylose,gaiactose, fructose,

maltose, glucose, sorbltol, dulcitol, arabitol and other sugar alcoholssuch as hexahydric alcohols derived from sugars, and other substanceshaving free hydroxy groups. The above polyglycerols and their oxidationproducts are produced by polymerizing glycerine, preferably by heatingwith about 1% of alkali at temperatures from 250 C. to 260 C. for aboutthree hours in the presence of an inert gas. This reaction mixture willgive a mixture of various polyglycerols, the size of the moleculesdepending upon the time of polymerization. The mixture of polyglycerolsis then oxidized with mild oxidizing agents to convert at least one ofthe primary hydroxy groups to a carboxylic group.

Examples of substances of my invention are as follows:

1. Tetraphosphoric acid ester of mono-olein,

ammonium salt. 2. Tetraphosphoric acid ester of diethylene glycolmono-ricinoleate, triethanolamine salt.

3. Tetraphosphoric acid ester of mono-laurin,

sodium salt.

4. Tetraphosphoric acid ester of mono-acetin,

sodium salt.

5. Tetraphosphoric acid ester of di-butyrin,

sodium salt.

6. Tetraphosphoric acid ester of cetyl ether of sorbitol.

'7. Tetraphosphoric acid ester of ethylene glycol mono-stearate.

8. Tetraphosphoric acid ester of ethyl ether of ethylene glycol.

9. Tetraphosphoric acid ester of octanoic acid ester of diethyleneglycol.

10. Tetraphosphoric acid ester of mixed cocoanut oil fatty acid ester ofdiethylene glycol, ammonium salt.

11. Tetraphosphoric acid ester of butyl ether of diethylene glycol,sodium salt.

12. Tetraphosphoric acid ester of sucrose monooleate, sodium salt.

13. Tetraphosphoric acid ester of mixed cocoanut oil fatty acid'monoordiglycerides or mixtures of monoand diglycerides, ammonium ortriethanolamine salts.

14. Di-tetraphosphorlc acid ester of sucrose distearate, ammonium salt.

15. Tetraphosphoric acid ester of mono-oleic acid ester of diglycerol,sodium salt.

16. Tetraphosphoric acid ester of mono-octyl ether of glycerol,potassium salt.

17. Tetraphosphoric acid ester of di-caproin,

sodium salt.

18. Di-tetraphosphoric acid ester of monocetyl glycerol, potassium salt.

19. Tetraphosphoric acid ester of lauryl ether of diethylene glycol,sodium salt.

20. Tetraphosphoric acid ester of mono-melissic acid ester of mannltol,ammonium salt.

21. Tetraphosphorlc acid ester of di-cetyl ether of sorbitol,monoethanolamine salt.

22. Tetraphosphoric acid ester of di-stearic acid ester of triglycerol,potassium salt.

23. Tetraphosphoric acid ester of mono-butyric acid ester of tartaricacid.

24. Tetraphosphoric acid ester of mono-propionic acid ester of mucicacid, sodium salt.

25. Tetraphosphoric acid ester of monoabietic acid ester ofglycerol,ammonium salt.

26. Tetraphosphoric acid ester of mono-benzoic acid ester of glycerol,sodium salt.

27. Tetraphosphoric acid ester of di-oleic acid ester of diethyleneglycol.

28. Tetraphosphoric acid ester of octyl alcohol.- 29. Tetraphosphoricacid ester of lauryl alcohol. 30. Tetraphosphoric acid ester of oieylalcohol. 31. Tetraphosphoric acid ester of stearyl alcohol. 32.Tetraphosphoric acid esters of mixture of. alcohols derived fromreduction of sperm oil. 33. Tetraphosphoric acid esters or mixture ofalcohols derived from reduction of cocoanut oil.

34. Tetraphosphoric acid ester of ricinoleyl alcohol. 35.Tetraphosphoric acid ester of butyl alcohol. 36. Tetraphosphoric acidester of cholesterol. The procedural details of the methods by means ofwhich the materials of my invention may be made may be varied. The exactmethod employed should be determined primarily by considering the typeof reacting constituents and the final substance to be produced. Inintroducing the tetraphosphate radical. for example, a materialcontaining an esterifiable hydroxy group is reacted with tetraphosphoricacid. Either one or more tetraphosphate radicals may be intro duced,depending upon the substance desired. Furthermore, the molal ratios ofthe reacting constituents may be varied to produce products havingvaried properties. A condensing agent and/or a solvent may be addedwhere required.

In order that those skilled in the art may even more fully understandthe scope of my invention, I shall describe various specific embodimentsof my invention in detail. It is to be understood, however, that thefollowing examples are given o'nly by way of illustration and are not tobe construed as limitative of the true scope of my invention which isset out in the appended claims. It is evident that proportions ofreacting ingredients, temperatures of reaction, time of reaction, andthe like represent factors which may be varied, all within the skill ofthose versed in the art in the light of my teachings herein.

Example I 50 parts by weight of monostearin were heated to degrees C.and to said monostearin was added slowly, while stirring, 50 partsby'weight of tetraphosphoric acid, previously heated to 90 degrees C.The temperature rose to about degrees C. and the mass became viscousandlight brown in color. Stirring was continued for several minutes untilthe product cooled down to approximately 90 degrees C. When the reactionmixture begins to drop in temperature, it is an indication that at leastthe major portion of the reaction has proceeded to completion. The finalproduct, which was practically odorless, very substantially reduced thespattering oi margarine and likewise reduced the surface tension ofwater.

Example II To 69 parts by weight of tetraphosphoric acid,-

Example III 26.8 parts by weight of oleic alcohol, previously heated toapproximately degrees C., were added slowly, with stirring, to 34.8parts by weight of tetraphosphoric acid, also previously heated to 90degrees C. The temperature rose to 125 degrees C. and, at thistemperature, the reaction product was a viscous mass, medium brown incolor. At room temperatures, the product became a heavy, nearly solidpaste.

Example IV 27 parts by weight of stearyl alcohol, previously heated toapproximately 90 degrees C., were added slowly, with vigorous stirring,to 34.8 parts by weight of tetraphosphoric acid, also previously heatedto approximately 90 degrees C. The temperature rose during the reactionto degrees C. at which point 18.2 parts by weight of pow- -deredmannitol were slowly added. The mass became thick and, upon stirring forseveral minutes, the reaction mass became much thinner. The product wasthen heated to 125 degrees C. for several minutes with vigorousstirring. The final product had many of the properties which have beendescribed hereinabove. In place of mannitol, other polyhydroxysubstances such as dextrose could be employed.

Example V 26 parts by weight of 2-ethyl hexanol-1 (betaethyl hexylalcohol), previously heated to 90 degrees C., were slowly added, withvigorous stirring, to 34.8 parts by weight of tetraphosphoric acid, alsopreviously heated to about 90 degrees C. The temperature rose toapproximately 125 degrees C. The reaction product was a liquid having amedium brown color.

Example VI 21 parts by weight of lauryl alcohol, previously heated to 90degrees C., were slowly added with stirring to 69.6 parts by weight oftetraphosphoric acid, also'previously heated to 90 degrees C. Thetemperature rose to degrees C. The reaction product was a yellow paste,soluble in water, and had excellent foaming properties. 20 parts byweight of the resulting product were dissolved in ether, the insolublematerial filtered on", and ammonia gas passed into the filtrate. Theresulting product, the ammonium salt of tetraphosphoric acid ester oflauryl alcohol, was an excellent foaming agent and possessed many of theother desirable properties described hereinabove.

Example VII 42 parts by weight of lauryl alcohol, previously heated to90 degrees C., were slowly added, with stirring, to 69.6 parts by weightof tetraphosphoric acid. The temperature rose to 125 degrees C. and thereaction product, at room temperatures, was a yellow paste. 32 parts byweight of triethanolamine were dissolved in 60 parts by weight of waterand 20 parts by weight of the above prepared reaction product were addedwith stirring at room temperature. The final solution was neutral tolitmus, was clear and transparent, and had excellent foaming propertiesrendering it especially adaptable for shampoos, detergents and the like.

Example vm 42 parts by weight of a product consisting essentially of themono stearic acid ester of diglyc- 62 parts by weight of dlolein,previously heated to 90 degrees C., were added slowly with stirring to34.8 parts by weight of tetraphosphoric acid. The temperature rose aftera few minutes to 126 degrees C. At degrees C. the reaction prodact was ared-brown liquid. on cooling, it became substantially thicker.

Example X 37 parts by weight of diethylene glycol monooleate, at 90degrees C., were slowly added, with stirring, to 34.8 parts by weight oftetraphosphoric acid, also at a temperature of about 90 degrees C. Thetemperature rise during the reaction was 55 degrees C. The resultingproduct was a chocolate-brown paste. By carrying out the reaction atlower temperatures, lighter colored reaction products are obtainable.

Example XI 30.8 parts by weight of mixed coconut oil mono fatty acidesters of diethylene glycol, at a temperature of about 90 degrees C.,were mixed with 34.8 parts by weight of tetraphosphoric acid, the esterbeing added to the acid as described in the above examples. Thetemperature rose to 136 degrees C., at which temperature the reactionproduct was a liquid of medium brown color. On cooling, it became apaste. This product was then neutralized in one case withtriethanolamine and in another case with mono-ethanol amine. In eachcase, products resulted having excellent foaming properties renderingthem especially adaptable for shampoos and detergents.

Example XII Example XIII 7 parts by weight of amylene and 34.8 parts byweight of tetraphosphoric acid were mixed-at room temperature (25degrees C.), the amylene being slowly added with stirring to thetetraphosphoric acid. The temperature rose to 65 degrees C. The reactionproduct was a viscous. red-colored liquid, very soluble in water.

While all of the substances of my invention fall into the category ofinterface modifiers, they modify an interface in various ways and tovarious extents, depending upon the relative potencies of the hydrophileand lipophile groups, the resultant of the two representing theinterfacial function of the molecule as a whole.

While the illustrative examples listed hereinabove represent in somecases single substances,

it must be understood that the'invention is by no means limited tosingle substances. Indeed.

in practice, it is frequently more convenient to prepare a mixture ofthe substances of my invention and to use such a mixture. For example, Imay prepare mixtures of monoglycerides and diglycerides of higher fattyacids by any convenient method, as, for example, by directesterification of glycerol with higher fatty acids or byreesteriiication of a triglyceride oil or fat with glycerol, preferablyin the presence of a catalyst, and then introduce into each member ofthis mixture of monoglycerides and di-glycerides a tetraphosphateradical. Moreover, in place of pure mono stearln, I may use a commercialproduct which contains small proportions of monopalmitin and mono-olein,or small proportions of the di-fatty acid esters of glycerin.

It is evident that I may prepare the ethers or the esters of thepolyhydroxy substances in any desired or known ways and subsequentlyesterify one or more of the remaining hydroxy groups of the polyhydroxysubstance to introduce therein the tetraphosphoric acid radical or,alternatively, I may first esterify the polyhydroxy substance withtetraphosphoric acid to form a tetraphosphoric acid ester and I may thenesterify or etherliy one or more of the remaining hydroxy groups of thepolyhydroxy substance by esterifying or etherifying procedures wellknown in the art.

The polyhydroxy substances which are the linking substances between thelipophile group or groups and the hydrophile tetraphosphate group may beconveniently considered as falling into two groups. The first of thesegroups includes compounds containing less than four esteriflable hydroxygroups and is exemplified by glycerine, glycol and polyglycols. Thesecond group contains those substances which have more than threeesterifiable hydroxy groups, examples of which are the sugars and sugaralcohols, the polyglycerols such as diand tri-glycerol, etc. It will beunderstood that my compounds may have one or more lipophile radicals andone or more hydrophile tetraphosphate radicals attached to thepolyhydroxy substance. Thus, for example, I may have themono-tetraphosphate of the dioleic acid ester of sucrose, or theditetraphosphate of the dioleic acid ester of sucrose. Similarly, I mayhave the di-stearic or other fatty acid ester of dior tri-glycerolmonoor ditetraphosphate. In a similar way, as described above, insteadof the acyl derivatives of the polyhydroxy substances I produce thecorresponding alkyl derivatives.

As I have described above, my compounds may contain either ester orether linkages. Any known methods of etherifying polyhydroxy substancesmay be employed. The following examples are illustrative:

Example-Sodium octyiate (CHr-CHr-CHz-CHzCEhJ tetraphosphate ester, bythe general procedure described in the examples listed hereinabove.

Example.Potassium cetylate (CH3(CH2) 14CH2-OK) is reacted with excessethylene glycol chlorhydrin by the procedure described in the aboveexample to form the glycol mono cetyl ether. This is then treated withtetraphosphoric acid to form a tetraphosphoric acid ester of cetylglycol ether. This may be neutralized with ammonia or some otheralkaline or potentially alkaline material to give salts of the cetylglycol ether tetraphosphate.

It must not be inferred that all or my compounds possess apolyhydroxy-residue linking the tetraphosphate radical with thelipophile radical. Although, for most purposes, I find such compounds tobe most eiilcacious, I wish also to include within the broader aspectsof my invention the tetraphosphoric acid esters of the straight orbranched chain aliphatic alcohols, particularly the higher molecularweight saturated and unsaturated aliphatic alcohols preferablycontaining at least six carbon atoms such as are derivable from naturaloils, fats and waxes such as lauryl alcohol, myristyl alcohol, oleyl,palmityl, stearyl; branched chain octyl alcohols like Z-ethyl hexanol-l;the alcohols derived from wool fat such as cholesterol; alcohols such asabietol, etc. Among these compounds are tetraphosphoric acid ester oflauryl alcohol, tetraphosphoric acid ester of oleyl alcohol (sodiumsalt), cholesterol tetraphosphate, etc. These compounds have been fullydescribed hereinabove and further elaboration appears to be unnecessary.

While my preferred compounds are tetraphcsphoric acid derivatives ofpolyhydroxy substances wherein at least one hydroxy group of thepolyhydroxy substance is esterified or etherifled with a groupcontaining at least four carbon atoms, and more desirably at least eightcarbon atoms, still, for some-purposes, the last mentioned group maycontain less than four carbon atoms as, for example, in the case of thetetraphosphoric acid ester of mono-acetin (sodium salt), number 4 in thelist of compounds mentioned above. Propionic acid and such lower fattyacids may be employed in partially esterlfying the polyhydroxy substancewhich may then be reacted to form the tetraphosphoric acid ester.

It will be noted, from the examples listed above, that thetetraphosphoric acid reacts with one or more hydroxy groups to form thetetraphosphoric acid ester. It is within the broader confines of myinvention, however, and as is evident in the light of the examplesdescribed above, to produce other types of compounds containing atetraphosphoric acid group. For example, in tri-olein, thetetraphosphoric acid radical adds on to the double bond of the oleicacid portion of the molecule. Other compounds of the same characterwhich react to add tetraphosphorlc acid at a double bond are monooleindi-stearate, corn oil, olive oil, cocoa butter, lard, unsaturatedhydrocarbons such as amylene, etc. In castor oil, for example, doublebonds and esteriilable hydroxy groups are both present.

Other compounds within the scope of my invention are tetraphosphoricacid esters of higher molecular weight hydroxycarboxylic acids. Ex-

amples of such acids are ricinoleic acid (previously mentioned),(ii-hydroxy stearic acid prepared by hydroxylation of oleic acid, andtrihydroxy stearic acid prepared by hydroxylation of ricinoleic acid.

In the neutralization of the tetraphosphate group or groups.considerable latitude and modification may be employed. While thetetraphosphate group may be left unneutralized, I find that, in general,the products are more suited to the purpose for which they are intendedif they are treated with a suitable inorganic or organic anti-acid agentto form the neutral'or acid salt. Examples of inorganic and organicanti-acid agents which may be used satisfactorily are bicarbonates ofthe alkali metals, potassium hydroxide, potassium carbonate, metallicsodium, sodium hydroxide, sodium oxide, sodium carbonate, ammoniumhydroxide, ammonia gas, and other anti-acid materials of the alkalineearth group, sodium stearate, calcium stearate, aliphatic and aromaticamines including tertiary amines, pyridine, quinaldine, alkylolamines,such as mono-, diand triethanolamine and mixtures thereof, quaternaryammonium bases such as tetramethyl and tetra-ethyl ammonium hydroxide,and also other anti-acid materials in which case hydrogen of thetetraphosphate group or groups is replaced by a cation such as sodium,potassium, ammonium, calcium, magnesium, aluminum, zinc, amines,alkylolamines, etc. It will be understood that by the term cation, asused throughout the specification and claims, is meant such elements asare mentioned herein and, in general, atoms or radicals which areregarded as bearing a positive charge. The tetraphosphoric ester may beneutralized to methyl orange, litmus, or phenolphthalein.

The products above described may be added in suitable proportions to atreating bath containing an aqueous medium, with or without anadditional substance, such as for example alkalis, mordants, dyes, colordischarging reagents, H202, color reducing agents, oils, sulphonatedoils, mordanting salts, and other reagents or substances used intreating baths, and the treating bath so formed can be employed withsatisfaction in the arts in which interface modification is desired. Forexample, dyeing, bleaching, scouring,

leather stufilng, and otherwise treating fabrics, fibers and othermaterials in a treating bath of this character is productive of goodresults. Also in the stuffing of leather, dyeing, and otherwise treatingfurs, and in many other arts, a treating bath employing the materials ofmy invention may be used. In flotation of ores it may be used by itselfor in connection with other reagents such as oleaginous agents ofvegetable or mineral origin, collecing agents such as fatty acids,depressants, etc.', to modify the interface between the finely dividedore and the aqueous medium. Various of the compounds of my inventionalso serve to increase the stability and modify the character of eggwhite foam made by beating egg whites or egg albumin.

While I have described various examples for the preparation of thematerials of my invention, it must be understood that the scope of theinvented class of substances is by no means limited by these methods.Other convenient methods may be used. This also applies, andparticularly so, to supplementary procedures of purification orisolation which lie strictly within the province of skill of anyqualified chemist whose procedures in each instance must be governed bythe properties of the materials concerned, and by the degree or thecharacter of the purity desired.

Wherever the prefix "poly is employed, it will be understood to meanmore than one.

The term residue., as used throughout the specification and claims, isemployed in its ordinarily understood chemical significance. For

example, where one of the hydroxy] groups of glycerine is esterifiedwith a fatty acid or etheriiied with an alcohol and another of thehydroxyl groups of the glycerine is esterified with tetraphosphoricacid, that which remains of the glycerine molecule, for example CHr- HOH

is the "residue of the polyhydroxy substance, in this case glycerine.

' The term higher, as used hereinabove and in the appended claims, willbe understood to cover at least six carbon atoms unless otherwisespecifically indicated.

What I claim as new and desire to protect by Letters Patent of theUnited States is:

1. A tetraphosphate of an aliphatic polyhydroxy substance wherein thehydrogen of at least one hydroxy group of the aliphatic polyhydroxysubstance is replaced by a radical selected from the group consisting ofalkyl and acyl radicals.

2. A tetraphosphate of an aliphatic polyhydroxy substance wherein thehydrogen of at least one hydroxy group of the aliphatic polyhydroxysubstance is replaced by a radical selected from the group consisting ofalkyl and acyl radicals containing at least four carbon atoms.

3. A tetraphosphate of an aliphatic polyhydroxy substance wherein thehydrogen of at least one hydroxy group of the aliphatic polyhydroxysubstance is replaced by a radical selected from the group consisting ofalkyl and acyl radicals, said polyhydroxy substance being a member ofthe group consisting of glycerol, glycols, polyglycerols, polyglycols,sugars, sugar alcohols, and hydroxycarboxylic acids.

4. A tetraphosphate of an aliphatic polyhydroxy substance wherein thehydrogen of atcleast one hydroxy group of the aliphatic polyhydroxysubstance is replaced by a radical selected from the group consisting ofalkyl and acyl radicals containing at least four carbon atoms, saidpolyhydroxy substance being a member of the group consisting ofglycerol, glycols, polyglycerols, polyglycols, sugars, sugar alcohols,and hydroxycarboxylic acids.

5. A tetraphosphate of a polyhydroxy substance wherein the polyhydroxysubstance has only one hydroxy group in which the hydrogen has beenreplaced by an acyl group containing at least four carbon atoms.

6. A tetraphosphate of an aliphatic polyhydric alcohol wherein at leastone hydroxy group of the alcohol has its hydrogen replaced by an acylgroup containing at least four carbon atoms. '7. A tetraphosphate of analiphatic polyhydric alcohol wherein at least one hydroxy group of thealcohol is esterified by a fatty acid contain- Cfl the fatty acidradical of which contains-at least six carbon atoms.

11. A tetraphosphate of an aliphatic dihydroxy substance, where thehydrogen 0! one hydroxy group is replaced by an acyl radical containingat least four carbon atoms.

12. A tetraphosphate of an aliphatic polyhydroxy substance with at leastfour carbon atoms and with at least two esterlfiable hydroxy groups,wherein the hydrogen of one hydroxy group is replaced by an acyl radicalwhich contains at least four carbon atoms.

13. A tetraphosphate of a polyhydroxy substance having not less thanfour esteriflable hydroxy groups, the hydrogen of at least one hydroxygroup being replaced by a radical selected from the group consisting ofalkyl and acyl radicals.

14. A poly-tetraphosphate of a polyhydroxy substance, the hydrogen of atleast one of said hydroxy groups being replaced by a radical selectedfrom the group consisting of alkyl and acyl radicals.

15. A tetraphosphate of a polyglycerol, the hydrogen of at least onehydroxy group of the polyglycerol being replaced by a radical selectedfrom the group consisting of alkyl and acyl radicals.

16. A tetraphosphate of an alcohol containing at least six carbon atoms.

17. A tetraphosphate of a straight chain aliamaeie phatio alcoholcontaining at least six carbon atoms.

18. A tetraphosphate of an aliphatic alcohol derived from natural fatsand oils and containing at least six carbon atoms.

19. A chemical compound represented by the general formula wherein Rrepresents a radical containing a hydrocarbon chain'of at least eightcarbon atoms, M is a tetraphosphoric acid group, Y is a cation, and w isa small whole number.

20. A chemical compound represented by the general formula wherein R.represents the radical of an aliphatic polyhydroxy substance wherein thehydrogen of at least one hydroxy group is replaced by an aliphaticradical containing at least eight carbon atoms, M is a tetraphosphoricacid group, Y is a cation, and w is a small whole number.

21. A reaction product of a tetraphosphate with an alkyl or acylderivative of a polyhydroxy substance, said derivative having at leastone hydroxy group in its molecule.

22. Tetraphosphates of mixed cocoanut oil mono-fatty acid esters of aglycol.

23. The product of claim 22 wherein the glycol is diethylene glycol.

MORRIS B. KATZMAN.

